How Do the Different Defect Structures and Element Substitutions Affect the Nonlinear Optical Properties of Lacunary Keggin Polyoxometalates? A DFT Study

Guan, Wei; Yang, Guochun; Yan, Lingling; Su, Zhong‐Min

doi:10.1002/ejic.200600450

Cited by 34 publications

(8 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Similar studies have also been conducted for functionalised Keggin structures 205,206 and for non-complete or lacunary anions. 207 Fig. 27 shows typical units of an organoimido derivative of POM as well as some typical relevant orbitals that are responsible for the charge transfer between the POM and the organic ligand and consequently for the b values.…”

Section: Miscellaneous Reactionsmentioning

confidence: 99%

Structure, properties and reactivity of polyoxometalates: a theoretical perspective

et al. 2012

View full text Add to dashboard Cite

In the thematic review dedicated to polyoxometalate (POM) chemistry published in Chemical Reviews in 1998, no contribution was devoted to theory. This is not surprising because computational modelling of molecular metal-oxide clusters was in its infancy at that time. Nowadays, the situation has completely changed and modern computational methods have been successfully applied to study the structure, electronic properties, spectroscopy and reactivity of POM clusters. Indeed, the progress achieved during the past decade has been spectacular and herein we critically review the most important papers to provide the reader with an almost complete perspective of the field.

show abstract

Section: Miscellaneous Reactionsmentioning

confidence: 99%

Structure, properties and reactivity of polyoxometalates: a theoretical perspective

et al. 2012

View full text Add to dashboard Cite

show abstract

“…49 DFT calculations highlight the reasons for differences of stability and redox potentials of Keggin-type POMs. [50][51][52][53][54][55][56][57][58][59][60] The voltammetric behaviour of some V V -POMs have been examined in aqueous electrolyte media, with reports in organic solvents being relatively rare. Recently, we quantitatively elucidated the voltammetric behavior of the vanadium component associated with reduction of [XVM 11 O 40 ] 4− (X = P, As; M = Mo, W), now designated as XVM 11 , in acidified CH 3 CN 61 and now turn our attention to the sulfur analogues whose properties are yet to be well established.…”

Section: Introductionmentioning

confidence: 99%

Structurally characterised vanadium(v)-substituted Keggin-type heteropolysulfates [SVM11O40]3− (M = Mo, W): voltammetric and spectroscopic studies related to the V(v)/V(iv) redox couple

Ueda

Nambu

et al. 2014

Dalton Trans.

View full text Add to dashboard Cite

Structures of the n-tetrabutylammonium salts of [SVM11O40](3-) (M = Mo, W) have been determined by X-ray crystallography and exhibit 3D networks with the V atom disordered over several sites. The cyclic voltammetric behavior of SVM11 in neutral and acidified acetonitrile solutions also has been investigated with respect to the V(V)/V(IV) couple. Results have been interpreted in conjunction with data provided by (51)V NMR spectroscopy on the oxidized V(V) form and by EPR spectroscopy on the reduced V(IV) form. Based on mechanistic details inferred from these studies, simulations of the cyclic voltammograms have been undertaken and results compared with experimental data in acidic media (two protonated forms) in order to provide estimates of equilibrium and kinetic parameters. For the V(V)/V(IV) couple in the series [XVM11O40](n-) (X = Si,Ge,P,As,S; M = Mo,W), the reversible potentials in neutral acetonitrile linearly depend on the total charge of the vanadium-substituted polyoxometalates, similar to the dependence previously reported for the non-substituted parent Keggin polyoxometalates [XM12O40](m-).

show abstract

“…Very recently, our group has been much interested in the investigations on the first and second hyperpolarizability of polyoxometalates and derivatives using density functional theory (DFT), which has emerged as currently the most applied method to investigate the properties of POMs . The main results are as follows: (1) The organoimido-to-polyanion charge transfer may be responsible for the NLO properties of this kind of compound.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Considerable Second-Order Nonlinear Optical Properties of Naphthylimido-Substituted Hexamolybdates

et al. 2008

View full text Add to dashboard Cite

The static first hyperpolarizabilities and origin of nonlinear optical (NLO) properties of [(2-methylnaphthyl)imido]hexamolybdates derivatives have been investigated by density functional theory (DFT). The [(2-methylnaphthyl)imido]hexamolybdate has considerable large first hyperpolarizability, 6.780 x 10(-30) esu, and it is larger than that of [(2,6-dimethylphenyl)arylimido]hexamolybdate due to the double aromatic rings in the naphthylimido ligand. The naphthylimido ligand acts as an electron-donor and the polyanion acts as an electron-acceptor. The substituent position on the naphthylimido is a key factor to determine the first hyperpolarizability of (naphthylimido)hexamolybdate derivatives. The derivative, which the iodine atom locates on the para nitrogen on the naphthylimido ligand, has the largest betao(o) value among the iodine-substituted derivatives. It suggests that the iodine atom is quasi linear with nitrogen and Mo, which is bonded to thenitrogen atom, could generate a large static electronic field and give the large contribution to NLO response.The introducing of electron-donors significantly enhances the first hyperpolarizabilities of (naphthylimido)hexamolybdates comparing with the electron-acceptors as the electron-donating ability is significantly enhanced when the electron-donor is attached to the naphthylimido segment. The present investigation provides important insight into NLO properties of (arylimido)molybdate derivatives.

show abstract

How Do the Different Defect Structures and Element Substitutions Affect the Nonlinear Optical Properties of Lacunary Keggin Polyoxometalates? A DFT Study

Cited by 34 publications

References 41 publications

Structure, properties and reactivity of polyoxometalates: a theoretical perspective

Structure, properties and reactivity of polyoxometalates: a theoretical perspective

Structurally characterised vanadium(v)-substituted Keggin-type heteropolysulfates [SVM11O40]3− (M = Mo, W): voltammetric and spectroscopic studies related to the V(v)/V(iv) redox couple

Theoretical Study on the Considerable Second-Order Nonlinear Optical Properties of Naphthylimido-Substituted Hexamolybdates

Contact Info

Product

Resources

About